131-58-8Relevant articles and documents
Palladium-catalyzed C-H acylation of arenes using thioethers as directing groups
Xu, Bo,Liu, Wei,Kuang, Chunxiang
, p. 2576 - 2583 (2014)
A highly efficient protocol for regioselective synthesis of diaryl ketones by palladium-catalyzed direct acylation of arenes using thioethers as directing groups is reported. The possible pathway of direct acylation between thioethers and α-oxocarboxylic acids is discussed. The direct acylation of thioethers via Pd-catalyzed C-H bond activation was described. Copyright
Application of mobilized gold nanoparticles as sole catalyst for the oxidation of secondary alcohols into ketones
Kidwai, Mazaahir,Bhardwaj, Saurav
, p. 1 - 4 (2010)
Oxidation of alcohols into corresponding ketones is efficiently catalyzed by heterogeneous gold nanoparticles. Use of H2O2 instead of O2 (g) is the main feature of our methodology since maintaining the required pressure of O2 (g) at elevated temperature is not easy. The reaction does not require any co-catalyst. After completion of the reaction, the catalyst could be recovered by centrifugation and reused several times with only a slight decrease in activity. Thus our present protocol, which is comprised of green reagent, solvent and catalyst, is completely clean.
Palladium NCN and CNC pincer complexes as exceptionally active catalysts for aerobic oxidation in sustainable media
Urgoitia, Garazi,Sanmartin, Raul,Herrero, Maria Teresa,Dominguez, Esther
, p. 2161 - 2166 (2011)
The oxidation of secondary benzyl alcohols is catalyzed by two palladacycles at atmospheric pressure in PEG-400, a sustainable reaction media. Recycling of the active catalytic species is performed up to the 5th run, and catalyst loadings decreased down to 10-8 mol%, thus achieving unprecedented TON and TOF values. In addition, the same conditions proved to be effective for the aerobic oxidation of benzyl methylene compounds, a scarcely explored process by palladium catalysts.
N-Acylsuccinimides: Twist-controlled, acyl-transfer reagents in Suzuki-Miyaura cross-coupling by N-C amide bond activation
Osumi, Yuki,Liu, Chengwei,Szostak, Michal
, p. 8867 - 8871 (2017)
The palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acylsuccinimides as versatile acyl-transfer reagents via selective amide N-C bond cleavage is reported. The method is user-friendly since it employs commercially-available, air-stable reagents and catalysts. The cross-coupling is enabled by half-twist of the amide bond in N-acylsuccinimides. These highly effective, crystalline acyl-transfer reagents present major advantages over perpendicularly twisted N-acylglutarimides, including low price of the succinimide activating ring, selective metal insertion under redox neutral conditions and high stability of the amide bond towards reaction conditions. Mechanistic studies indicate that oxidative addition is the rate limiting step in this widely applicable protocol.
Sulfated fibrous ZrO2/Al2O3 core and shell nanocomposites: A novel strong acid catalyst with hierarchically macro-mesoporous nanostructure
Liu, Erming,Locke, Ashley J.,Frost, Ray L.,Martens, Wayde N.
, p. 95 - 105 (2012)
A series of solid strong acid catalysts were synthesized from fibrous ZrO2/Al2O3 core and shell nanocomposites. In this series, the zirconium molar percentage was varied from 2% to 50%. The ZrO2/Al2O3 nanocomposites and their solid strong acid counterparts were characterised by a variety of techniques including 27Al magic angle spinning nuclear magnetic resonance (MAS-NMR), scanned electronic microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and infrared emission spectroscopy (IES). NMR results show that the interaction between zirconia species and alumina strongly correlates with pentacoordinated aluminium sites. This can also be detected by the change in binding energy of the 3d electrons of the zirconium. The acidity of the obtained solid acids was tested by using them as catalysts for the benzoylation of toluene. It was found that a sample with a 50% zirconium molar percentage possessed the highest surface acidity equalling that of pristine sulfated zirconia despite the reduced mass of zirconia.
Bismuth(III) bis(trifluoromethanesulfonyl)amide
Picot, Alexandre,Repichet, Sigrid,Le Roux, Christophe,Dubac, Jacques,Roques, Nicolas
, p. 129 - 134 (2002)
Bismuth(III) bis(trifluoromethanesulfonyl)amide (Bi(NTf2)3, 3) has been prepared from the reaction of protiodemetallation of tri-p-tolylbismuth by a stoichiometric amount of bis(trifluoromethanesulfonyl)amine (1). The intermediates BiPh3-n(NTf2)n (n=2 (4), 1 (5)) resulting from the reaction of 1 with triphenylbismuth have also been isolated. The amide 3 was able to catalyze the benzoylation and the benzenesulfonylation of toluene.
Light/Palladium-Promoted Benzylic C?H Acylation Using a Benzoyl Group as the Photo-Directing Group
Masuda, Yusuke,Ishida, Naoki,Murakami, Masahiro
, p. 403 - 406 (2019)
2-Methylphenyl ketones undergo site-selective acylation at the benzylic position when treated with acid anhydride under UV irradiation in the presence of a palladium catalyst. The benzoyl carbonyl group serves as the photo-directing group so that the ortho benzylic C?H bond is activated site-selectively.
REVERSAL OF THE BENZOPHENONE REACTIVITY UPON η2 -COMPLEXATION TO BIS( η5 -CYCLOPENTADIENYL)ZIRCONIUM
Rosenfeldt, Frank,Erker, Gerhard
, p. 1637 - 1640 (1980)
Reversal of the carbonyl activity of benzophenone, serving as electron donor in single-electron transfer processes and acting as a proton acceptor through the 'carbonyl'carbon atom, is observed upon η2 -complexation to zirconocene.
Protocol for Palladium/ N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Cross-Coupling of Amides by N-C(O) Activation
Lei, Peng,Li, Guangchen,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
, p. 682 - 687 (2020/11/23)
Amides are among the most important and ubiquitous functional groups in organic chemistry and process development. In this Practical Synthetic Procedure, a protocol for the Suzuki-Miyaura cross-coupling of amides by selective N-C(O) bond activation catalyzed by commercially available, air-and moisture-stable palladium/N-heterocyclic carbene (NHC) complexes is described. The procedure described involves [Pd(IPr)(cin)Cl] [IPr = 2,6-(diisopropylphenyl)imidazol-2-ylidene, cin = cinnamyl] at 0.10 mol% at room temperature and is performed on decagram scale. Furthermore, a procedure for the synthesis of amide starting materials is accomplished via selective N-tert-butoxycarbonylation, which is the preferred method over N-Acylation. The present protocol carries advantages of operational simplicity, commercial availability of catalysts, and excellent conversions at low catalyst loadings. The method is generally useful for activation of N-C(O) amide bonds in a broad spectrum of amide precursors. The protocol should facilitate the implementation of amide cross-coupling reactions.
Poly(ethylene glycol) dimethyl ether mediated oxidative scission of aromatic olefins to carbonyl compounds by molecular oxygen
Yu, Tao,Guo, Mingqing,Wen, Simiaomiao,Zhao, Rongrong,Wang, Jinlong,Sun, Yanli,Liu, Qixing,Zhou, Haifeng
, p. 13848 - 13852 (2021/04/22)
A simple, and practical oxidative scission of aromatic olefins to carbonyl compounds using O2as the sole oxidant with poly(ethylene glycol) dimethyl ether as a benign solvent has been developed. A wide range of monosubstituted,gem-disubstituted, 1,2-disubstituted, trisubstituted and tetrasubstituted aromatic olefins was successfully converted into the corresponding aldehydes and ketones in excellent yields even with gram-scale reaction. Some control experiments were also conducted to support a possible reaction pathway.